The nuclear disaster at the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March 2011 caused partial meltdowns of three reactors. During the meltdowns, a type of condensed particle, a caesium-rich micro-particle (CsMP), formed inside the reactors via unknown processes. Here we report the chemical and physical processes of CsMP formation inside the reactors during the meltdowns based on atomic-resolution electron microscopy of CsMPs discovered near the FDNPP. All of the CsMPs (with sizes of 2.0–3.4 μm) comprise SiO2 glass matrices and ~10-nm-sized Zn–Fe-oxide nanoparticles associated with a wide range of Cs concentrations (1.1–19 wt% Cs as Cs2O). Trace amounts of U are also associated with the Zn–Fe oxides. The nano-texture in the CsMPs records multiple reaction-process steps during meltdown in the severe FDNPP accident: Melted fuel (molten core)-concrete interactions (MCCIs), incorporating various airborne fission product nanoparticles, including CsOH and CsCl, proceeded via SiO2 condensation over aggregates of Zn-Fe oxide nanoparticles originating from the failure of the reactor pressure vessels. Still, CsMPs provide a mechanism by which volatile and low-volatility radionuclides such as U can reach the environment and should be considered in the migration model of Cs and radionuclides in the current environment surrounding the FDNPP.

Highly radioactive cesium-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) provide nano-scale chemical fingerprints of the 2011 tragedy. U, Cs, Ba, Rb, K, and Ca isotopic ratios were determined on three CsMPs (3.79–780 Bq) collected within ~10 km from the FDNPP to determine the CsMPs’ origin and mechanism of formation. Apart from crystalline Fe-pollucite, CsFeSi2O6 · nH2O, CsMPs are comprised mainly of Zn–Fe-oxide nanoparticles in a SiO2 glass matrix (up to ~30 wt% of Cs and ~1 wt% of U mainly associated with Zn–Fe-oxide). The 235U/238U values in two CsMPs: 0.030 (±0.005) and 0.029 (±0.003), are consistent with that of enriched nuclear fuel. The values are higher than the average burnup estimated by the ORIGEN code and lower than non-irradiated fuel, suggesting non-uniform volatilization of U from melted fuels with different levels of burnup, followed by sorption onto Zn–Fe-oxides. The nano-scale texture and isotopic analyses provide a partial record of the chemical reactions that occurred in the fuel during meltdown. Also, the CsMPs were an important medium of transport for the released radionuclides in a respirable form.

Trace U was released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) during the meltdowns, but the speciation of the released components of the nuclear fuel remains unknown. We report, for the first time, the atomic-scale characteristics of nanofragments of the nuclear fuels that were released from the FDNPP into the environment. Nanofragments of an intrinsic U-phase were discovered to be closely associated with radioactive cesium-rich microparticles (CsMPs) in paddy soils collected ∼4 km from the FDNPP. The nanoscale fuel fragments were either encapsulated by or attached to CsMPs and occurred in two different forms: (i) UO nanocrystals of ∼70 nm size, which are embedded into magnetite associated with Tc and Mo on the surface and (ii) Isometric (U,Zr)O nanocrystals of ∼200 nm size, with the U/(U+Zr) molar ratio ranging from 0.14 to 0.91, with intrinsic pores (∼6 nm), indicating the entrapment of vapors or fission-product gases during crystallization. These results document the heterogeneous physical and chemical properties of debris at the nanoscale, which is a mixture of melted fuel and reactor materials, reflecting the complex thermal processes within the FDNPP reactor during meltdown. Still CsMPs are an important medium for the transport of debris fragments into the environment in a respirable form.

Highly radioactive cesium-rich microparticles (CsMPs) were released from the Fukushima Daiichi nuclear power plant (FDNPP) to the surrounding environment at an early stage of the nuclear disaster in March of 2011; however, the quantity of released CsMPs remains undetermined. Here, we report a novel method to quantify the number of CsMPs in surface soils at or around Fukushima and the fraction of radioactivity they contribute, which we call "quantification of CsMPs" (QCP) and is based on autoradiography. Here, photostimulated luminescence (PSL) is linearly correlated to the radioactivity of various microparticles, with a regression coefficient of 0.0523 becquerel/PSL/h (Bq/PSL/h). In soil collected from Nagadoro, Fukushima, Japan, CsMPs were detected in soil sieved with a 114 μm mesh. There was no overlap between the radioactivities of CsMPs and clay particles adsorbing Cs. Based on the distribution of radioactivity of CsMPs, the threshold radioactivity of CsMPs in the size fraction of <114 μm was determined to be 0.06 Bq. Based on this method, the number and radioactivity fraction of CsMPs in four surface soils collected from the vicinity of the FDNPP were determined to be 48-318 particles per gram and 8.53-31.8%, respectively. The QCP method is applicable to soils with a total radioactivity as high as ∼10 Bq/kg. This novel method is critically important and can be used to quantitatively understand the distribution and migration of the highly radioactive CsMPs in near-surface environments surrounding Fukushima.

Radioactive Cs isotopes (137 Cs, t 1/2 = 30.07 years and 134 Cs, t 1/2 = 2.062 years) occur in severely contaminated soils within a few kilometer of the Fukushima Daiichi nuclear power plant at concentrations that range from 4 × 10 5 to 5 × 10 7 Bq/kg. In order to understand the mobility of Cs in these soils, both bulk and submicron-sized particles elutriated from four surface soils have been investigated using a variety of analytical techniques, including powder X-ray diffraction analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and analysis of the amount of radioactivity in sequential chemical extractions. Major minerals in bulk soil samples were quartz, feldspar, and minor clays. The submicron-sized particles elutriated from the same soil consist mainly of mica, vermiculite, and smectite and occasional gibbsite. Autoradiography in conjunction with SEM analysis confirmed the association of radioactive Cs mainly with the submicronsized particles. Up to~3 MBq/kg of 137 Cs are associated with the colloidal size fraction (<1 μm), which accounts for~78% of the total radioactivity. Sequential extraction of the bulk sample revealed that most Cs was retained in the residual fraction, confirming the high binding affinity of Cs to clays, aluminosilicate sheet structures. The chemistry of the fraction containing submicron-sized particles from the same bulk sample showed a similar distribution to that of the bulk sample, again confirming that the Cs is predominantly adsorbed onto submicron-sized sheet aluminosilicates, even in the bulk soil samples. Despite the very small particle size, aggregation of the particles prevents migration in the vertical direction, resulting in the retention of >98% of Cs within top~5 cm of the soil. These results suggest that the mobility of the aggregates of submicron-sized sheet aluminosilicate in the surface environment is a key factor controlling the current Cs migration in Fukushima.